Mixture of filaments capable of being dyed to a multicolor pattern with anionic disperse dyes

ABSTRACT

The present invention relates to a process for dyeing fibers, fabrics or other shaped articles made from blends of either poly(alpha-olefins) or polyesters and various thermoplastic nitrogen-containing basic polymers to a multicolor pattern.

United States Patent Farber et al.

[151 3,652,198 1*Mar. 28, 1972 [54] MIXTURE OF FILAMENTS CAPABLE OFBEING DYED TO A MULTICOLOR PATTERN WITH ANIONIC DISPERSE DYES [72]Inventors: Milton Farber, Verona, N.J.; Robert Miller; Charles N. Brown,both of Colum- [21] Appl.No.: 759,776

[52] US. Cl ..8/15, 8/31, 8/39,

8/100, 8/42 D, 8/168, 8/180, 57/140 [51] Int. Cl ..D06p 5/02, D06p 1/16[58] Field ofSear-ch ..8/l80, 100, 115.5, 168,21,

[56] References Cited UNITED STATES PATENTS 3,215,487 11/1965 Cappuccioet al.... .....8/1l5.5 3,329,557 7/1967 Magat et a1 161/172 3,337,6528/1967 Press 8/168 X 3,361,843 1]] 968 Miller et al 260/857 3,375,2133/1968 Press ..8/l73 X 3,439,999 4/1969 Miller ..8/l5

Primary Examiner-George F. Lesmes Assistant ExaminerPatricia C. IvesAttorney-Thomas A. Beck [57] ABSTRACT The present invention relates to aprocess for dyeing fibers, fabrics or other shaped articles made fromblends of either 1 poly(a1pha-olefins) or polyesters and variousthermoplastic nitrogen-containing basic polymers to a multicolorpattern.

50 Claims, No Drawings Cappuccio et a1. ..18/54 MIXTURE F FILAMENTSCAPABLE OF BEING DYED TO A MULTICOLOR PATTERN WITH ANIONIC DISPERSE DYESThe process of the present invention consists of treating shapedarticles made from poly(alpha-olefins) or polyesters and a thermoplasticnitrogen-containing basic polymer in discontinuous fashion with a Lewisacid composition which optionally may contain anionic dyes, anionicsurfactants and other modifiers, and then subsequently dyeing thetreated article, if said anionic dyes are not used in the Lewis acidcomposition. Due to differences in affinity for different classes ofdyes between treated and untreated areas of the shaped articles,multicolor dyeings will be obtained. The present invention thus providesa method of treatment for imparting local differences in affinity fordifferent dye classes to a filamentary assembly, which term is used todenote a fiber, yarn, fabric or other shaped article, so that byexposure of such fiber, yarn, fabric or article, either at the time oftreatment or subsequently, to dyes of different classes, a multicoloreffect will be obtained.

The base material used in this invention is an inherently undyeable ordifficult to dye fiber, yarn, fabric or other shaped article made from apoly(alphaolefin) or polyester. By blending this inherently undyeablematerial with a minor amount of a thermoplastic nitrogen-containingbasic polymer capable of binding both disperse and anionic dyes, suchmaterial is made dyeable with disperse dyes, but is still impermeableand hence undyeable with anionic dyes. When fibers, yarns, fabrics orother shaped articles are made from the above-described blends, andlocalized areas of said articles are treated with Lewis acid or Lewisacid generating material compositions as described herein, the treatedareas are rendered highly dyeable with anionic dyes. Dyeing the treatedarticles with anionic and optionally disperse dyes, either at the timeof treatment or subsequently, yields a multicolor effect, since thetreated areas are dyeable with both anionic and disperse dyes, whereasthe untreated areas are dyeable only with disperse d es.

The process of the present invention includes the following steps asexplained herein:

1. Blending between about 0.5 and 5 percent of a thermoplasticnitrogen-containing basic polymer capable of binding anionic (i.e.,acid-type) dyes, and optionally between about 0.5 and 5 percent of ahydrophilic compound containing ethylene oxide groups, with afiber-forming poly(alphamonoolefin) or polyester.

2. Forming said resulting blend into a fiber, yarn, fabric or othershaped article.

3. Optionally dyeing said shaped article with a disperse dye.

4. Contacting desired portions of said shaped article with an activatingamount (i.e., an amount sufficient to impart permeability to anionicdyes) of a Lewis acid composition which optionally contains a thickeningagent, an anionic surfactant and anionic dyes.

5. If desired, heating said shaped article in contact with said Lewisacid composition to accelerate penetration of the Lewis acid compositioninto the shaped article.

6. Removing the excess of Lewis acid composition from the treatedarticle by rinsing, soaping, scouring or the like.

7. Dyeing the treated article, if desired, with an anionic dye, eitheralone or simultaneously or consecutively with a different disperse dye,if the article was previously dyed with a disperse dye.

U.S. Pat. No. 3,361,843 and U.S. Pat. No. 3,432,250 filed Mar. 16, 1964,both by Robert Miller, Frederick C. Loveless and Milton Farber, describeprocesses whereby undyeable or difficult to dye hydrocarbon highpolymers and polyesters are rendered deeply dyeable by anionic dyes towhich they are normally inert without deleteriously affecting thephysical properties of the articles formed from the polymer. Briefly,the processes entail incorporating a minor amount of a thermoplasticnitrogen-containing basic polymer in the poly(alpha-monoolefin) ofpolyester and, subsequent to the formation of fibers or other articlesfrom the polymeric compositions, treating them with a Lewis acid capableof reacting with the basic polymer to form'an acid-base reactionproduct. This treatment renders these articles highly dyeable withanionic dyes.

As is explained in the above-mentioned disclosures, the incorporation ofminor amounts of thermoplastic nitrogen-containing basic polymers in apolyolefin or polyester does not render fibers, yams, fabrics or othershaped articles formed from such a polymeric composition substantiallydyeable by anionic dyes. Such dyes will only impart very pale tints tosuch articles, so that for all practical purposes, they canbe said to besubstantially undyeable by acid-type dyes. Such articles, however, aresubstantially susceptible to dyeing by other classes of dyes, mainly thedisperse dyes.

After the treatment with Lewis acids (activation).of articles made frommixtures of polyolefins or polyesters with minor amounts (between 0.5 to10 percent, but preferably 0.5 to 5 percent, since there is some uptakeof anionic dye at the higher levels) of the basic nitrogen-containingpolymers according to the process of the said patent and pendingapplication, these fibers become highly susceptible to dyeing by anionicdyes and can readily be dyed to desirable deep shades by them.

Copending U.S. patent application Ser. No. 679,618, by Andor Schwarcz,filed Nov. 1, 1967, now U.S. Pat. No. 3,530,201, describes the use ofhydrophilic compounds containing ethylene oxide units along with thebasic nitrogen-containing polymers to yield acid-dyeable shaped articlesand fibers from poly-alpha-olefins and polyesters.

According to copending patent application Ser. No. 705,303, filed Feb.14, 1968, by Andor Schwarcz and Charles Brown, application of anionicsurfactants under acid conditions greatly enhances the uptake of anionicdyes by fibers or other shaped articles made from blends of alpha-olefinor polyester polymers with minor amounts (0.5 to 5 percent) ofthermoplastic nitrogen-containing basic polymers and, optionally,similar amounts (0.5 to 5 percent) of hydrophilic compounds containingethylene oxide units.

Copending U.S. Pat. No. 3,439,999 to RobertMiller and Milton Farber,describes a method of attaining a multicolor effect from a single dyeingstep by dyeing fabrics containing yarns made according to U.S. Pat. No.3,361,843 or U.S. Pat. No. 3,432,250 and other yarns not treated withthe Lewis acid.

We have now discovered a new and novel method for producing multicoloreffects on fibers, yarns or other shaped articles made from the abovedescribed modified polyolefins or polyesters. For the purposes ofdiscussion in this disclosure this method is entitled discontinuousactivation, which means that the fiber, or shaped article is treatedwith the Lewis acid only in certain areas or portions of the fiber,fabric or article, according to the wishes of the processor. When thearticle treated in this fashion is subsequently exposed to a dyebath,only the activated areas (i.e., areas treated by discontinuousactivation) will absorb anionic dyes, whereas both treated and untreatedareas will absorb disperse dyes. The

result will be a two-color dyed effect. When more than two colors aredesired this may be achieved by mixing different dyes separately withthe Lewis acid and applying each mixture of dye-Lewis acid separately tothe article. Still another means for attaining multicolor effects wouldbe by including natural (i.e., uncolored) or pigmented yarns in apolyolefin or polyester fabric. Tone-on-tone effects, i.e., differentintensities of the same color, may also be achieved alone or incombination with multicolor effects, by using combinations of fibers inthe yarn or fabric, wherein one fiber is made from a polyolefin orpolyester containing dye receptor alone and the other fiber frompolyolefin or polyester containing both dye receptor and hydrophiliccompound containing ethylene oxide groups. The first fiber would bealmost wholly undyeable with anionic dyes, while the second would havesignificant dyeability with anionic dyes. The activated portions of thetwo .poly( 3-methyll-butene fibers will show a similar difference indyeability with anionic dyes as do the unactivated counterparts. Theresultant product thus shows a tone-on-tone effect.

In the present invention, the shaped articles, fabrics or fibers madefrom alpha-monoolefin polymers comprise a major portion of inherentlyundyeable alphamonoolefin polymers comprising both homopolymers andcopolymers of alpha-monoolefins; for example, copolymers withnon-terminal olefins or with one or more other alpha-olefins, as well asblock copolymers of alpha-olefins with each other and graft copolymersof alpha-olefins with polymers of other alphaolefins. The class includespolyethylene, polypropylene, poly(4-methyll -pentene), copolymers ofpropylene and 4-methyl-l-pentene, and copolymers of any of the foregoingmonomers with each other The vinyl-substituted monocyclic and polycyclicpyridine base dye-receptor polymers may be incorporated in the and/orwith other copolymerizable monomers. The preferred material of thisclass is polypropylene, by which we mean any polymer of propylene andany copolymer containing predominantly polymerized propylene togetherwith any other comonomer copolymerized therewith.

The term polyester as used herein refers to polymers which arecondensation polymers of dihydric alcohols with organo-dibasic acids ortheir anhydrides, particularly dicarboxylic acids, and self-condensationpolymers of omega-hydroxy carboxylic acids. The preferred polyestermaterials in our in- 1 vention are poly(ethylene terephthalate),poly(ethylene terephthalate-isophthalate), andpoly(l,4-cyclohexylenedimethylene terephthalate), and further discussionin terms of polyesters will be mainly in terms of these representativepolyesters. It will be understood however, that the invention isapplicable'to'all fiber-forming polyesters, in which the ester linkagesare intralinear, including poly(alkylene alkanedioates),poly(cycloalkylenedimethylene alkanediotes), poly(alkylenearenedioates), poly(cycloalkylenedimethylene arenedioates), andanalogous materials. Examples of the above-named polyesters arerespectively, poly(ethylene adipate), p0ly( l,4-cyclohexylenedimethylene adipate), poly(ethylene terephthalate), andpoly(l,4-cyclohexylenedimethylene terephthalate).

The basic dye receptor polymers which may be incorporated in thepolyolefins or polyesters listed previously are thermoplastic basicnitrogen-containing materials capable of binding anionic and dispersedyes, and are illustrated by:

1. Polymers of vinyl-substituted monoand polycyclic pyridines, eitherhomopolymers or copolymers with each other, or with other vinylcompounds, including graft copolymers.

2. Polyamides, including condensation homopolymers and copolymers, inwhich the amide groups are an integral part of the polymer chain, andaddition homopolymers and copolymers having pendant groups containing orconsisting of amide groups.

3. Amine polymers, including condensation homopolymers and copolymers,in which the amine group is an integral part of the polymer chain, andaddition homopolymers and copolymers having pendant groups which includeor consist of amine groups.

Other basic nitrogen polymers which may be used in this process arepolyurethanes, poly(vinylcarbazoles), aniline-formaldehyde resins, etc.The major requirement for the type of structure of this nitrogencontaining material is that it be capable of binding anionic dyes.

The basic nitrogen polymers employed should not be extractable from themixtures thereof with the polyolefin or polyester under the conditionsof treating and dyeing used, since of course this would lower oreliminate the dyeability. As a diagnostic test, a l-hour extraction ofthe fiber or shaped article with boiling water at a pH of 3 for 1 hourshould not extraet more than 90 percent of the originally added nitrogenpolymer. The amount of the basic nitrogen polymer added to thepolyolefin or polyester polymer should be sufiicient so that, after theacid treatment of the invention, it will bind the amount of dye requiredto produce the shade desired.

hydrocarbon polymer either as a homopolymers, or as a copolymer withanother vinyl-substituted pyridine or with any other vinyl monomercopolymerizable therewith, or as a graft copolymer with a hydrocarbonhigh polymer. The vinyl-substituted monoand polycyclic pyridine base dyereceptor polymers used are those based, for example, ormonovinylpyridines and monovinylquinolines.

The monovinylpyridines useful in making the above named dye-receptivepolymers employed in the invention include 2- vinylpyridine,3-vinylpyridine, 4-vinylpyridine, S-methyl-Z- vinylpyridine,2-ethyl-5-vinylpyridine, pyridine, 2-ethyl-6-vinylpyridine,2-isopropenylpyridine, etc. Polymerizable olefinic monomers with whichthe monovinylpyridine may be copolymerized include acrylic andmethacrylic esters typified by ethyl acrylate and methyl methacrylate,vinyl aryl hydrocarbons typified by styrene and vinyltoluenes, andbutadiene--l,3. Alternatively,.the monovinylpyridine may begraft-copolymerized, by well-known methods, with a previously formedlinear high polymer, typified by polyethylene, polypropylene,polystyrene, and polybutadiene. ln instances where a hydrophiliccompound containing ethylene oxide units (-CH -CH -O-) is incorporatedinto blends containing a polyolefin or a polyester it is preferable toemploy nitrogen base polymers containing pyridinic groups only, (i.e.,ones which are not copolymerized with non-nitrogen base monomers.) It isalways desirable that the basic polymer contain no more than a minorproportion of non-basic material copolymerized with a monovinylpyridine,since only the pyridine portion of the polymer additive is active inenhancing dyeability.

The polyamides useful as the dye-receptors employed in this processinclude homopolyamides such as poly(hexamethylene adipamide),poly(hexamethylene sebacamide), polypyrrolidinone, polycaprolactam,polyenantholactam, and copolyamides such as Zytel 61 (a trademark of duPont de Nemours and Company), an interpolymer of hexamethylene adipamideand hexamethylene sebacamide with caprolactam.

As examples of vinyl polymers with pendant groups consisting of orcontaining amide groups there are the substitutedpoly(vinylpyrrolidinones), (e.g., polymers ofN-vinyl-3-alkylpyrrolidinone) and N-substituted polyacrylamides, (e.g.,N- butylacrylamide). Also usable are copolymers of the amidecontainingvinyl monomers with other olefinic monomers such as acrylic andmethacrylic esters typified by ethyl acrylate and methyl methacrylate,vinylaryl hydrocarbons typified by styrene and vinyltoluenes, andbutadiene-l,3. Alternatively, the vinylpyrrolidinones or acrylamides maybe graftcopolymerized, by well-known methods, with a previously formedlinear high polymer, typified by polyethylene, polypropylene,polystyrene, and polybutadiene. It is always desirable that the basicpolymer contain no more than a minor proportion of materialcopolymerized with the vinylpyrrolidinones or acrylamides, since onlythe amide portion of the polymer additive is active in enhancing thedyeability of the hydrocarbon polymer.

As examples of amine polymers useful as the dye receptor employed inthis invention there are the condensation products of epihalohydrins ordihaloparafiins with one or more amines, such as those disclosed inBelgian Pat. No. 606,306, exemplified by the condensation product ofdodecylamine, piperazine and epichlorohydrin; as examples of additionpolymers with pendant groups consisting of or containing amines thereare the reaction product of a styrenemaleic anhydride copolymer with3-(dimethylamino) propylamine (the product being a polyamino-polyimide),and styrene-allylamine copolymers such as those disclosed in U.S. Pat.No. 2,456,428.

The hydrophilic compounds, optionally blended in the amounts of about0.5 and 7 percent with the hydrocarbon polymer or polyester used in thisinvention, are selected from the following groups of compounds:

2-methyl-5-vinyll. Polyethylene glycol (also referred to herein as PEG)having a degree of polymerization (DP) of at least 4.

2. Copolymers of ethylene oxide with other alkylene oxides having adegree of polymerization of the ethylene oxide units of at least 4 andcontaining a minimum of 60 percent by weight ethylene oxide. Thesecompounds are exemplified by the series of block copolymers produced bycondensing ethylene oxide with a product formed by the condensation ofpropylene oxide with propylene glycol (formula of such copolymers: HO(CH O) ,.(C H O),H) and sold under the trademark Pluronic). Other usefulcopolymers are derived from the polymerization of ethylene oxide andpropylene 0xide.

3. Derivatives of polyethylene glycol, such as its ethers and estershaving a degree of polymerization of ethylene oxide of at least 4 and anethylene oxide content of at least 60 percent by weight. Examples ofsuch derivatives are: (a) polyethylene glycol alkyl ethers; (b)alkylaryl polyethoxyalcohols sold under the trademark Triton"(octylphenylpolyethoxy ethanol series); (c) polyoxyethylene derivativesof long chain fattyacid esters of hexitol anhydrides includingsorbitans, sorbides, mannitans and mannides, such as polyethylene glycolhexitol carboxylates, polyoxyethylene sorbitan' monolaurate sold underthe trademark Tween and polyoxyethylene sorbitan monostearate; andpolyethylene glycol carboxylate esters such as polyethylene polyethyleneglycol distearate.

The mixtures of the hydrocarbon polymer or polyester and thenitrogen-containing dye receptor polymers are made by blending, tumblingor any convenient method and then can be shaped by vacuum molding,extrusion or in the case of fibers, may be spun into yarns using aconventional melt spinning process. The articles made from the polymerblend are treated with the Lewis acid composition after shaping. If thearticle to be treated is a fabric made from yarns, the physical form ofsaid fibers which are woven into the fabric may vary widely. They may bemonofilament or multifilament; plain, bulked or texturized; staple, towor stock. The treatment with the Lewis acid composition may be done inany convenient fashion such as roller printing, screen printing,spraying or dipping. By means known to those skilled in the art, randomor regular color effects can be produced. If a sharply defined patternor design is desired, a thickener which is compatible with the Lewisacid may be employed to prevent migration, which is the tendency of theapplied activating material to diffuse or wick away from the site oforiginal application and thus produce a blurred rather than a sharplydefined area. The duration of the acid activation treatment with theLewis acid composition may be from a few seconds to several hours, butfor practical reasons is preferably kept between 10 seconds to minutesduration. In order to hasten diffusion of the Lewis acid and the othermodifiers present in the activating material into the treated article,it may be heated at a temperature below the melting temperature of thematerial. Usually a temglycol monostearate and perature not greater than140 C. for poly(alpha-olefins) and a 200 C. for polyesters issatisfactory and sufficient in most cases.

The activating material which is used in accordance with the presentinvention, may contain, in addition to the Lewis acid, an anionicsurfactant, an anionic dyestufi and a suitable amount of water andthickening agent to form a paste of desired consistency. The followingare examples of the Lewis acids which may be used in the presentinvention. They are illustrative and in no way limiting:

l. Concentrated inorganic acids such as hydrochloric acid, hydrobromicacid, sulfurous acid, nitric acid, sulfuric acid, phosphoric acid andperchloric acid, or the anhydrides thereof.

2. Organic carboxylic and sulfonic acids including aliphatic, aromatic,hydroxy-substituted aromatic acids, monocarboxylic and dicarboxylicacids, monosulfonic and disulfonic, saturated and unsaturated acids.Suitable acids are exemplified by formic, acetic, propionic, stearic,and other alkanoic acids in the C C range, undecylenic, oleic, benzoic,salicyclic, succinic, adipic, phthalic, bromoacetic, benzenesulfonic,ptoluenesulfonic, chloroacetic and lactic acids.

Examples of preferred acids used in the present invention arehydrochloric, formic, acetic, monoor dichloroacetic andpara-toluenesulfonic acids. Any Lewis acid or Lewis acid generatingmaterial which can be applied to the yarn, fabric or shaped article maybe used, including hydrolyzable halides such as aluminum, zinc and tinhalides, benzylic halides, allylic halides, acyl halides and sulfonylhalides, phenols, borate esters and the like. The acid may be used inthe liquid or molten state (when its melting point is below thetemperature selected for the treatment) or in solution in an aqueous ororganic solvent. The concentration of the Lewis acid used in theactivating composition of the present invention is not critical sincelow concentrations of the acid may be applied in solution in a volatilesolvent, with the solvent being evaporated during the heating period.Concentrations of Lewis acid in the activating composition of between 4and percent (on the weight of treating composition) are the mostconvenient, when used in the absence of anionic surfactants. Lowerconcentrations (i.e., between about 0.l and 4 percent) as well as thehigher ones are operative in the presence of anionic surfactants.

The anionic surfactants optionally employed in the present inventionhave the general formula (R-A) wherein R represents a hydrophobic groupwhich is either a substituted or non-substituted alkyl, aryl, oralkylaryl group having six or more carbon atoms (preferably between nineand 40 carbon atoms) per A group; and A is an anionic group exemplifiedby one or more of the following groups:-(l) sulfonate; (2) sulfate; (3)phosphate or polyphosphate; 4) carboxylate etc. The A group can be inthe free acid form or in the salt form, but acid conditions (i.e., a pHof about 5 or less) must always be present. Another type of anionicsurfactant which can be used is one wherein R may contain apolyoxyalkylene group. Additional operative materials include thosegenerating anionic surfactants in situ during the process of thisinvention. Examples of useable anionic surfactants are:

Commercial Name Sodium laurylsulfate Sodium tetradecylsulfate Sodiumcetylsulfate Aerosol TR Aerosol OT Aerosol AY TergitOl l5-S-3A TetgitollS-S-3S Sandopan 6624 Victawet 35B Barisol Super BRM Alkapent CCAlkapent M60 Chemsol 700-S Chemsol 935-N Estranol CP Alkapent A GafacRS-6l0 Gafac 1.0-529 Zelek UN Chemical Description C,,H,,SO Na C I-I SONa C H SO Na Bis(tridecyl) ester of sodium sulfosuccinic acid Dioctylester of sodium sulfosuecinic acid Diamyl ester of sodium sult'osuccinicacid rs x1 )n SO NH,

r s) Coconut oil fatty acid amine condensate Potassium salt of aphosphated alcohol Phosphated ethoxylated oleyl alcoholOrgano-phosphmacid Solar 25 Laureltex 802 Rozak BD-l Fosterage LF AcidSeycopen BB Phosphnted polyalcohol Crestol Phosphated complex 21- coholWarcosol NF/3 Complex of sulfonated polyester and phosphated alcoholSurfactant 05-44 Phosphated ester, free acid Detergent 9294 Anionicphosphate ester Seyco Phosphonic Acid Aromatic phosphated ester, freeacid Anionic surfactants, when used in the activating composition ofthis invention, permit the use of lesser amounts and a lowerconcentrations of Lewis acid as described above. Any concentration aboveabout 0.5 percent of anionic surfactant in the Lewis acid treatingcomposition is operative but concentrations in said composition betweenabout 0.5 and'5 percent are preferred. Attendant to this are savings incost, the use of less expensive metals and alloys in storage andapplication equipment, decreased corrosion anclv lower toxicity hazards.Their incorporation in the activating composition is thus highlybeneficial. v I

The Lewisacid-containing activating compositions of the presentinvention are frequently applied by conventional textile printingtechniques which involve thickening them so they spreading of theapplied pattern, as desired. Other dyeing assistants, such as retardingagents, wetting agents and leveling agents may likewise be added to theactivating paste in accordance with the effects to be obtained.

When dyeing is subsequent to activation, a two-color dyed effect may berealized with the treated yarn, fabric or shaped article. Byincorporating dyes in the activating paste, however, multiple-passprinting techniques may be used with different dyes in separate pastesto achieve multicolor eflects. By dyeing the entire fabric with adisperse dye prior to activation, and then printing with the activatingpaste, over-printed ef-' fects may be obtained. Swelling agents(carriers) to open the fiber to dyes, such as ortho-dichlorobenzene,aromatic hydrocarbons, etc. may be used in the paste, but the effect ofthe present invention does not depend upon the use of a carrier. Thefollowing anionic dyes can be utilized in the practice of the presentinvention:

Strong Acid Dyes Acid Yellow 23 (Cl. No. 19140) Acid Orange 7 (CI. No.15510) Acid Red 73 (CI. No. 27290) Acid Blue 25 (Cl. No. 62055) AcidBlue 78 (CI. No. 62105) Acid Metallized Dyes Acid Yellow 54 (C1. No.19010) Acid Orange 72 (CI. No. 18740) Acid Red 186 (C1. No. 18810) AcidRed 212 Acid Blue 158 (CI. No. 14880) Acid Black 52 (CI. No. 15711)Neutral Metallized Dyes Acid Yellow 121 (C. 1. No. 18690) Acid Orange 60(The half-chrome complex of l-phenyl-3- methyl-4-(2-hydroxy-5-sulfamoylphenylazo)-5- pyrazolone) Acid Red 209 Acid Blue 168 Acid Black 60Another category of anionic dyes which may be used in this invention arethe direct dyes typified by the following:

Direct Yellow 44 (CI. No. 29000) Direct Red 13 (CI. No. 22155) DirectBlue 67 (Cl. No. 27925 Other categories of anionic dyes which areapplicable to our invention are the reactive dyes, typified by ReactiveOrange 1, and the mordant acid dyes, typified by Mordant Red 3 (O1. No.5 8005 In addition to anionic dyes, disperse dyes may also be used inthe present invention, as previously described. Examples of this classare:

Disperse Yellow 23 (Cl. No. 26070) Disperse Orange 21 Disperse Blue 27(CI. No. 60667) Cibacete Pink FG Disperse Yellow 42 (CJ. No. 10338)Interchem Blue RLF 40 As indicated herein previously the dye penetrationintothe Lewis acid-treated yarn fabric or shaped article is increased 7and deeper colors are produced when the activating paste is heated. Thiscan be accomplished by heating the fabric or shaped article with thepaste thereon to a temperature below the melting point of the polymersused (i.e., to 200 C.), or the paste may be heated prior to applicationto the article. If the paste includes a dye, both activation and dyeingare accelerated by the heating step. Otherwise, dyeing is carried outsubsequent to the treatment, which has the practical advantage than anundyed fabric may be stored and then dyed to any desired two- (ormulticolor with natural or pigmented yarns) shade as needed. For theheating step, either steam or dry heat may be used. Steam at about 100C. for 3 to 20 minutes is, however, preferred for optimum results.

The following examples are included to illustrate but not necessarily tolimit our invention.

EXAMPLE 1 A blend of 97.1% isotactic polypropylene and 2.9 percentpoly-2-vinylpyridine was melt-spun into fiber, drawn 5:1 and theresultant yarn knit into tubular fabric.

An activating paste was prepared by mixing 100 grams of 90 percentformic acid, 10 grams of hydroxyethylcellulose and 10 grams water. Theactivating paste was printed on a sample of the tubular fabric in theform of an X. The treated fabric was then heated on a ferrotype plate at260 F. for 10 minutes, and then rinsed in water containing a smallamount of nonionic detergent which is the nonylphenol/ethylene oxidecondensate known as Triton X-100. After being scoured at 93 C. for 20minutes in water at pH 10 containing a small amount of nonionicdetergent, the fabric was dyed for 1 hour at 200 F in a dyebathcontaining 3 percent owf (on the weight of fiber) Capracyl Orange R(Acid Orange 60) and 3 percent owf Calcosperse Yellow 4 RL (DisperseYellow 23). The fabric was finally post-scoured for 10 minutes at F. inwater containing a small amount of nonionic detergent.

The sample was dyed orange where the acid-containing activation pastehad been applied and yellow where it had not been applied. The contrastwas marked and the borders were clearly defined.

EXAMPLE 2 The procedure of Example 1 was duplicated except thatmethylcellulose was used as thickener, and spots of paste, rather thanan X, were applied to the fabric. After scouring, the fabric was dyed asin Example 1, using only Capracyl Orange R. After dyeing, orange spotsresulted where the paste had been applied, while the untreated areaswere colored only a very pale pink.

An intimate mixture of 97.1 percent isotactic polypropylene and 2.9percent poly(2-viny1pyridine) was melt-spun and drawn into a 52-filament4,000 denier yarn. Three of these yarns were plied together, texturized,and tufted into jute carpet backing. The tufted carpet was thensimultaneously activated and dyed using the following procedure:

The face yarn of the carpet was printed with a paste made up of 3percent Neolan Red BRE (Acid Red 212), 5 percent Lyogen VU (a nonionicalkylphenolpolyether glycol used as levelling agent), 5 percent Polygum261, a purified natural gum ether thickening agent, 6 percent formicacid and 81 percent water. The carpet containing the paste thereon wasput into a saturated steam atmosphere at 212 F. for 20 minutes, removedfrom the atmosphere and scoured for five minutes at 140 F. with anaqueous solution containing 0.5 percent owf Triton X-100. A carpethaving a red pattern printed on it resulted, with good patterndefinition of the printed area and negligible migration into andstaining of the unprinted area.

EXAMPLE 4 A carpet prepared as in Example 3 was printed with pastecontaining 3 percent Crocein Scarlet SS (Acid Red 73, C.l. No. 27090), 5percent Polygum 261, anatural purified gum ether thickening agent, 40percent of a 1:1 mixture of monochloroand dichloroacetic acid, 7 0.1percent Triton X-100 and 51.9 percent water. The carpet containing thepaste was put into a superheated steam atmosphere at 120 C. for 3%minutes and scoured for 5 minutes with an aqueous solution of 0.5percent owf Triton X-100 at 140 F. The resultant carpet had a printedscarlet pattern with deep color penetration and negligible dye migrationand staining to the untreated areas.

EXAMPLE 5 A carpet prepared as in Example 3 was printed with a pastecontaining 3 percent Cibalan Grey BL (Acid Black 60), 5 percent Polygum261, a natural purified gum ether thickener, 40 percent of a 1:1 mixtureof monochloroand dichloroacetic acid, 0.1 percent Triton X-100 and 51.9percent water. The carpet containing the paste was put into asuperheated steam atmosphere at 120 C. for 3% minutes. It was thenremoved from the steam atmosphere and scoured for 5 minutes with anaqueous solution of 0.5 percent owf Triton X-l at 140 F. The resultantcarpet had a printed grey pattern with deep color penetration andnegligible dye migration and staining to the untreated areas.

EXAMPLE 6 A carpet prepared as in Example 3 was printed with pastecontaining 3 percent Pilate Fast Blue RRN (an acid metallized anionicdye), percent Polygum 261, a natural purified gum ether thickener, 40percent of a 1:1 mixture of monochloroand dichloroacetic acid, 0.1%Triton X-100 and 51.9 percent water. The carpet containing the paste wasput into a superheated steam atmosphere for 3% minutes at 120 C. It wasthen removed from the steam atmosphere and scoured for 5 minutes with anaqueous solution of 0.5 percent owf Triton X-l 00 at 140 F. Theresultant carpet had a printed blue pattern with deep color penetrationand negligible dye migration and staining to the untreated areas.

EXAMPLE 7 A carpet prepared as in Example 3 was printed with a pastecontaining 2% percent Carbolan Brilliant Blue 2-GS (a strong acid typeanionic dye), 2% percent formic acid, 2% percent of an anionicsurfactant made from the reaction of fatty alcohols with phosphoruspentoxide, and 92.5 percent water. The printed carpet was heated at 212F. by steam for minutes in a closed chamber, and then rinsed in watercontaining 0.5 percent owf nonionic surfactant at 180 F. for minutes.The

resultant carpet was dyed to a deep blue shade in the areas where thedye paste has been applied, and sharp definition of the printed patternwas obtained without staining of adjacent untreated material.

EXAMPLE 8 This example illustrates the technique in the presentinvention of overprinting with an acid dye on a previously dispersedyedbackground. For this purpose, a sample of carpet prepared by the sameprocedure as in Example 3 from a blend of 2.9 percent of the 1:1copolymer of Z-vinylpyridine. and 2- methyl-S-vinylpyridine with 97.1percent isotactic polypropylene was dyed with 0.25 percent owf ofTerasil Blue GLF (Disperse Blue 27, CI. 60767) in conventional fashion,using 1 percent owf acetic acid in the dye bath and dyeing at the boilfor 1 hour. The dyed carpet was then postscoured and dried.

The light blue product was then screen printed with the fol lowing pasteformulation:

1 percent Wool Yellow (Acid Yellow 23, CI. 19140) 3 percentDiethanolamine salt of a 1:1 mixture of monoand di-fatty alcoholphosphates 5 percent Formic acid 2.5 percent Polygum 275 88.5 percentwater (percentages are on the weight of paste) The printed carpet wassteamed for 10 minutes at 105 C. and post-scoured, yielding a greenprint on a light-blue background. The printed pattern was sharplydefined with deep color penetration.

EXAMPLE 9 This example illustrates the technique in the presentinvention of overprinting with an acid dye on an acid-dyed background. Asample of the carpet used in Example 8 was prescoured and dyed with thefollowing dyebath:

1 percent owf Carbolan Brilliant Blue 268 (Acid Blue 4 percent owfSodium laurylsulfate 5 percent owf Acetic acid 0.5 percent owf Lyogen MS(a cationic leveling agent for anionic dyes) The carpet was dyed for 1hour at the boil, rinsed, postscoured and dried. It was medium blue incolor.

The dyed carpet was then roller printed with the same paste used inExample 8 and aftertreated in the same fashion as the printed carpet inExample 8. The resultant product had a green pattern on a medium bluebackground, the pattern being sharply defined and deeply dyed.

EXAMPLE 10 This example illustrates printing with a mixture of Lewisacid and anionic surfactant, followed by dyeing with a mixture of acidand disperse dyes. A sample of the carpet used in Example 8 was screenprinted with the following paste:

4 percent Tergitol l5-S-3S 3 percent para-Toluenesulfonic acid 3 percentPolygum 275 90 percent Water The printed carpet was steamed andscouredas in Example 8. It was then dyed in the following dyebath for one hourat the boil:

1 percent owf Alizarine Cyanine Green G (Acid Green 25,

CI. 61570) 0.25 percent owf Terasil Blue GLF (Disperse Blue 27, CI.

3.0 percent owf Acetic Acid 0.5 percent owf Lyogen MS After scouring,the product was a carpet of blue background with a green pattern. Thepattern was clearly defined and deeply dyed.

A carpet yarn made from a blend of 97 percent isotactic polypropyleneand 3 percent of a copolymer composed of 75 percent2-methyl-5-vinyl-pyridine and 25 percent styrene was tufted into carpetand dyed to a light yellow color in the following dyebath:

0.20 percent owf Wool Yellow (Acid Yellow 23, C.l.

19140) 3.0 percent owf Sandopan 6624 (C,,H, -,(CH CH,O)

CH,COONa) 5.0 percent owf Acetic acid After dyeing for 45 minutes at theboil, the carpet was postscoured and dried. It was then roller printedwith the following composition:

1 percent Anthraquinone Blue percent Sodium cetylsulfate 5 percentFormic acid 3.75 percent Polygum 275 85.25 percentWater SWE (Acid Blue25, C. l.

The printed carpet was steamed for 3 minutes in a superheated steamatmosphere and then postscoured. It had a green pattern of gooddefinition on-a yellow background.

EXAMPLE 12 I A sample of the carpet described in Example 1 1 was dyed toa medium yellow shade with 0.5 percent owf Calcosperse Yellow 4RL(Disperse Yellow 23, C.l. 26070). When printed with the paste describedin Example 11, followed by steaming and postscouring as in Example 8, agreen pattern on a yellow background was obtained.

EXAMPLE 13 A sample of the carpet described in Example 1 l was printedwith a paste containing 40 percent of a 1:1 mixture of monoanddichloroacetic acids, 5 percent Polygum 261 and 55 percent water. Theprinted carpet was steamed for 3% minutes at 120 C., postscoured anddyed with the dyebath of Example 1. An orange print on a yellowbackground was obtained. Example 14 A blend of 100 parts of isotacticpolypropylene, 3.5 parts of the 1:1 copolymer of 2-vinylpyridine with2-methyl-5-vinylpyridine and 2 parts of polyethylene glycol of molecularweight 600,000 was converted to carpet yarn by the procedure of Example3 and tufted into jute carpet backing. Samples of this carpet whentreated according to the procedures of Examples 8, 9 and 10 gave resultssimilar to those described in these examples except that the colors weredarker.

EXAMPLE This example demonstrates the process of the present in ventionin making effects of more than two colors by multiple over-printing. Asample of the carpet described in Example 8 was pad-dyed with thefollowing composition:

1.0 percent Capracyl Orange R (Acid Orange 60) 3.0 percentDiethanolamine salt of a 1:1 mixture of monoand di-fatty alcoholphosphates 5.0 percent Formic acid The carpet was padded with the abovecomposition to ca. 100 percent wet pickup, steamed 10 minutes at 100-105C., postscoured and dried.

It was then screen printed with three different screens, each screenhaving a pattern which was not coincident with either of the other twoscreens. The printing pastes all contained 3 percent Polygum 275, 5percent formic acid, dye and water to i make 100%. The following dyeswere separately used in the above paste formulation to make the threeoverprints:

Supralan Yellow NR (a neutral metallized dye, Acid Yellow 12l,C.l.18690) Calcocid Brown RD (Acid Brown 14, C.l. 20195) Buffalo Black SS(Acid Black 1,C.l. 20470) After steaming for 10 minutes at 100-105 C.,the printed carpet was postscoured and dried. The multicolor pattern wasblack, brown and orange on a reddich orange background.

EXAMPLE 16 A blend of 100 parts of polyethylene terephthalate, 2 partsof poly-2-vinylpyridine and 6 parts of polyethylene glycol of molecularweight 4 million was melt-spun at 540 F. into 70- filament yarn anddrawn 4 to l to form a final yarn of 20 denier per filament. Two ofthese yarns were then plied together, texturized and the texturized yarntufted into jute carpet backing. To form the background color, thecarpetwas dyed for minutes at the boil with the following dyebath:

0.75 percent owf Cibacete Orange 2RN (Disperse Orange 0.50 percent owfAcetic acid 2.0 percent owf Diammonium phosphate 0.5 percent Lyogen MSThe orange-dyed carpet was postscoured and dried. It was then screenprinted with the following composition:

1 percent Anthraquinone Blue SKY (Acid Blue 78, C.l. 62105) 5 percentFormic acid 3 percent Diethanolamine salt of a 1:1 mixture of mono-.

and di-fatty alcohol phosphates 3 percent Polygum 260- 88 percent waterThe printed carpet was steamed for 12 minutes at 100 C. and thenpostscoured, yielding a product having a green print on an orangebackground.

EXAMPLE 17 A sample of the carpet used in Example 16 was dyed for onehour at the boil with the following dye bath:

0.75 percent owf Alizarine Blue SAP (Acid Blue 45, C.l.

63010) 5 percent owf Formic acid 3 percent owf Sodium laurylsulfate 0.5percent owf Triton X-l 00 The dyed carpet was postscoured, dried andscreen printed with the following formulation:

1 percent Wool Yellow (Acid Yellow 23, C.l. 19140) 10 percent 1:1mixture of monoand dichloroacetic acids 3.2 percent Polygum 260 85.8percent Water The printed carpet was steamed for 10 minutes and scouredyielding a product having a green pattern of sharp definition on a bluebackground.

EXAMPLE 18 EXAMPLE 19 A sample of the carpet used in Example 16 wasroller printed with the acid paste used in Example 1 8, steamed for 5minutes at C. and then scoured. When dyed with l percent owf CarbolanBrilliant Blue 208 (Acid Blue in the presence of percent acetic acid,the resultant carpet was colored medium blue with a dark blue pattern.

EXAMPLE 20 A sample of the carpet used in Example 16 was screen printedwith the following paste:

5 percent Formic acid 3 percent Diethanolamine salt of a 1:1 mixture ofmonoand di-fatty alcohol phosphates 3.5 percent Polygum 260 88.5 percentWater The printed carpet was steamed for minutes at 100 C., scoured anddyed with the same dyebath as used in Example 10. After scouring, thepolyester carpet had a sharply defined green print on a blue background.

EXAMPLE 21 Three batches of print paste and dye were made up, eachcontaining 100 parts of the paste used in Example 20 and one part ofdye. The batches contained the following dyes:

Batch No. 1: Buffalo Black SS (Acid Black 1, C.I.20470) Batch No. 2:Calcocid Brown RD (Acid Brown 14, CI.

Batch No. 3: Capracyl Orange R (Acid Orange 60).

The three batches of paste were separately printed, using silk screenswith non-coincident patterns, on a sample of the polyester carpet usedin Example 16. The printed carpet was steamed for 5 minutes at 120 C.,scoured and dried. It had a printed pattern of black, brown and orangeon a white background.

EXAMPLE 22 A sheet of 300 of the 52-filament 4,000 denier yarns preparedin Example 3 was randomly printed with the acid paste of Example 13,steamed for 4 minutes at 120 C., scoured and dried. The yarn was thentufted into jute carpet backing and the resultant carpet dyed in a bathidentical with the one used in Example 10. After scouring, the productwas a space-dyed carpet composed of random blue and green colored areas.

EXAMPLE 23 A sheet of yarns identical with those used in Example 21 wassuccessively randomly printed with three different pastes. The pastesall contained the ingredients of the paste used in Example 10, to whichwas added 3 percent of the following d es:

Paste A: Crocein Scarlet SS (Acid Red 73, C]. No. 27090) Paste B: WoolYellow (Acid Yellow 23, C.I. 19140) Paste C: Alizarine Cyanine Green G(Acid Green 25, CI.

The printed sheet was then steamed for 4 minutes at 120 C., scoured anddried. The yarns were then tufted into jute carpet backing to yield aspace-dyed carpet which was composed of red, yellow, green, orange,chartreuse and gray areas.

Having thus described our invention, what we claim and desire to protectby Letters Patent is:

l. A mixture of filaments capable of being dyed to a multicolor patternthrough exposure to anionic and disperse dyes, said filaments havingbeen prepared from a blend comprising:

A. a fiber-forming poly(alpha-olefin) or polyester,

B. between about 0.5 and 5 percent of a thermoplasticnitrogen-containing basic polymer capable of binding anionic dyes,

wherein at least some of the filaments contained in said mixture arecontacted discontinuously along their length with between about 4 andless than 100 percent on weight of the fiber, of a concentrated Lewisacid or Lewis acid-generating material of sufficient concentration toform a reaction product with said nitrogen-containing polymer, saidtreatment occurring prior to or during the dyeing step and resulting inthe portions of said filaments so treated being dyeable with anionic anddisperse dyes, and the portions of said filaments not so treated beingdyeable with disperse dyes only.

2. The mixture of filaments defined in claim 1, in which the blendcontains between about 0.5 and 7percent by weight of a hydrophiliccompound which is a homopolymer of ethylene oxide, an ether or esterderivative thereof, or copolymer of ethylene oxide, said hydrophiliccompound having a degree of polymerization not less than 4, and anethylene oxide content not less than percent by weight, the total amountof the thermoplastic nitrogen-containing polymer and said hydrophiliccompound in said blend being greater than 3 percent by weight of totalblend.

3. The mixture of filaments of claim 1 wherein the poly(alpha-olefin) isselected from polyethylene, polypropylene, poly( 3-methyl-l-butene) orpoly(4-methyl-lpentene) and the polyester is selected from the poly(ethylene terephthalate ),poly( 1 ,4-cyclohexylene-dimethyleneterephthalate).

4. The mixture of filaments of claim 1 wherein the basicnitrogen-containing polymer is selected from the group consisting ofhomopolymers of vinylpyridinesyalkylvinylpyridines,

vinylquinolines, alkylvinylquinolines, or'copolymers of vinylpyridinemonomers with each other or with alkylvinylpyridine monomers, orcopolymers of vinylpyridine monomers with each other or withalkylvinylpyridine monomers, or copolymers of vinylpyridine monomerswith a monoethylenically unsaturated monomer.

5. The mixture of filaments of claim 4 which is a yarn.

6. The mixture of filaments of claim 4 which is a fabric.

7. The mixture of filaments of claim 4 which is included in a carpet.

8. The fabric of claim 6 which contains uncolored non-dyereceptor-containing poly(alpha-olefin) or polyester fibers which are notsusceptible to dyeing by anionic and disperse dyes under the conditionsof dyeing.

9. The carpet of claim 7 which contains uncolored non-dyereceptor-containing poly(alpha-olefin) or polyester fibers which are notsusceptible to dyeing by anionic and disperse dyes under the conditionsof dyeing.

10. The fabric of claim 6 which contains pigmented poly(alpha-olefin) orpolyester fibers which are not susceptible to dyeing by anionic anddisperse dyes under the conditions of dyeing. A

11. The carpet of claim 7 which contains pigmented poly(alphwolefin) orpolyester fibers which are not susceptible to dyeing by anionic anddisperse dyes under the conditions of dyeing.

12. The fabric of claim 8 which contains pigmented poly(alpha-olefin) orpolyester fibers which are not susceptible to dyeing by anionic anddisperse dyes under the conditions of dyeing.

13. The carpet of claim 9 which contains pigmented poly(alpha-olefin) orpolyester fibers which are not susceptible to dyeing by anionic anddisperse dyes under the conditions of dyeing.

.the poly(alpha-olefin) is selected from the group consisting ofpolyethylene, polypropylene, poly(3-methyl-l-butene) orpoly(4-methyl-l-pentene) and the polyester is selected from the groupconsisting of poly(ethylene terephthalate), poly(ethyleneterephthalate-isophthalate) or 'poly(l,4- cyclohexylene-dimethyleneterephthalate.)

- with said mixture.

16. The mixture of filaments of claim 15 in which the Lewis acid orLewis acid-generating material is selected from the group consisting ofa. Concentrated inorganic acids, or their anhydrides.

b. Organo-carboxylic or sulfonic acids c. Hydrolyzable halides d. Borateesters e. Phenol l7.' The mixture of filaments of claim 16 which hasbeen treated under acid conditions with an anionic surfactant eitherprior to or during said Lewis acid or Lewis acid-generating materialtreatment, said anionic surfactant having the general formula R-Awherein:

R represents a substituted or unsubstituted alkyl aryl, or alkylarylgroup having at least six carbon atoms and A represents an anionic groupselected from (a) sulfate, (b)

sulfonate, (c) phosphate, (d) polyphosphate or (e) carboxylate.

18. The mixture of filaments of claim 17 which has been treated with amixture of 0.1 percent or greater of Lewis acid or Lewis acid-generatingmaterial based on the total treating composition weight, and greaterthan 0.5 percent of said anionic surfactant based on the total treatingcomposition weight and a viscosity increasing agent.

19. The mixture of filaments of claim 18 in which said mixture containsan anionic dyestufi.

20. The mixture of filaments of claim 19 which hasbeen dyed with ananionic or disperse dyestufi' prior to treatment 21. The mixture offilaments of claim 2 wherein the poly( alpha-olefin) selected frompolyethylene, polypropylene, poly(3-methyl-l-butene) orpoly(4-methyl-l-pentene and the polyester is selected from poly(ethyleneterephth'alate), poly(ethylene terephthalate-isophthalate) or poly( 1,4-cyclohecylene-dimethylene terephthalate). g 22. The mixture of filamentsof c'laim2 wherein the basic nitrogen-containing polymer is selectedfrom the group consisting of homopolymers ofvinylpyridines,'alkyivinylpyridines, vinylquinolines,alkylvinylquinolines, or copolymers of vinylpyridine monomers with eachother or with alkylvinylpyridine monomers, or copolymers ofvinylpyridine monomers with a monoethylenically unsaturated monomer.

23. The filamentary assembly of claim 22 which is a yarn.

24. The mixture of filaments of claim 22 which is a fabric.

25. The mixture of filaments of claim 22 which is included in a carpet.

26. The fabric of claim 24 which contains uncolored nondyereceptor-containing poly(alpha-olefin) or polyester fibers which are notsusceptible to dyeing by anionic and disperse dyes under the conditionsof dyeing.

27. The carpet of claim 25 which contains uncolored nondyereceptor-containing poly( alphaolefin) or polyester fibers which are notsusceptible to dyeing by anionic and disperse dyes under the conditionsof dyeing.

28. The fabric of claim 24 which contains pigmented poly(alpha-olefin)or polyester fibers which are not susceptible to dyeing by anionic anddisperse dyes under the conditions of dyeing.

29. The carpet of claim 25 which contains pigmented poly(alpha-olefin)or polyester fibers which are not susceptible to dyeing by anionic anddisperse dyes under the conditions of dyeing.

30. The fabric of claim 26 which contains pigmented poly(alpha-olefin)or polyester fibers which are not susceptible to dyeing by anionic anddisperse dyes under the conditions of dyeing.

31. The carpet of claim 27 which contains pigmented poly(alpha-olefin)or polyester fibers which are not susceptible to dyeing by anionic anddisperse dyes under the conditions of dyeing.

32. The mixture of filaments defined in claim 22 in which the basic dyereceptor polymer is selected from the group consisting of:

a. poly(2'vinylpyridine) b. poly( 2-methyl-5-vinylpyridine) c.poly(4-vinylpyridine) d. poly( 2-vinylquinoline) e. .the copolymer of 2-vinylpyridine and Z-methyI-S-vinylpyridine f. the copolymer of2-vinylpyridine and styrene g. the copolymer of 2-methyl-5-vinylpyridineand styrene.

33'. The shaped article of claim 32 in which the poly(alphaolefin) isselected from the group consisting of polyethylene, polypropylene,poly(3-methyl-l-butene) or poly(4-methyl-lpentene) and the polyester isselected from the group consisting of poly(ethylene terephthalate),poly(ethylene terephthalate-isophthalate) or poly( l,4-cyclohexylene-dimethylene terephthalate).

, 34. The mixture of filaments of claim 33 in which the Lewis acid orLewis acid-generating material is selected from the group consisting ofa. Concentrated inorganic acids or their anhydrides. b.Organo-carboxylic or sulfonic acids.

c. Hydrolyzable halides.

d. Borate esters,

e. Phenol.

'35. The mixture of filaments of claim 34 which has been treated underacid conditions with an anionic surfactant either prior to or duringsaid .Lewis acid or Lewis acid generating material treatment, saidanionic surfactant having the general formula R-A wherein:

R represents a substituted or unsubstituted alkyl, aryl, or alkylarylgroup having at least six carbon atoms and A represents an anionic groupselected from (a) sulfate, (b)

sulfonate (c) phosphate, (d) polyphsophate or (e) carboxylate.

36. The mixture of filaments of claim 35 which has been treated with amixture of 0.1 .percent or greaterof Lewis acid or Lewis acid-generatingmaterial based on the total treating composition weight, and greaterthan 0.5 percent of said anionic surfactant based on the total treatingcomposition weight and a viscosity increasing agent. 7

37. The mixture of filaments of claim 36 in which said mixture containsan anionic dyestufi.

38. The mixture of filaments of claim 37 which has been dyed with ananionic or disperse dyestuff prior to treating with said mixture.

39. A process for making the mixture of filaments defined in claim 1comprising the following steps in sequence:

a. blending between about 0.5 and 5 percent of a thermoplasticnitrogen-containing basic polymer capable of binding anionic dyes with afiber-forming poly(alphaolefin) or polyester,

b. forming the resulting blend into fiber,

c. forming said fiber into a mixture of filaments,

d. discontinuously contacting the surface of said filaments with atreating composition which contains between about 4 percent and percentof a Lewis acid or Lewis acid generating material,

e. heating said mixture of filaments containing the treating compositionfor such time to allow penetration of same,

f. removing the excess treating composition,

g. dyeing the treated filaments with an anionic dyestuff alone or incombination with a disperse dyestuff.

40. The process defined in claim 39, in which between about 0.5 and 7percent by weight of a hydrophilic compound has been added to the blendprior to forming said blend into fiber, said hydrophilic compound beinga homopolymer of ethylene oxide, an ether or ester derivative thereof,or copolymer of ethylene oxide, said hydrophilic compound having adegree of polymerization not less than 4, and an ethylene oxide contentnot less than 60 percent by weight, the total amount of thethermoplastic nitrogen containing polymer and hydrophilic compound insaid blend being greater than 3 percent by weight of the total blend.

41. The process defined in claim 39 in which an anionic dye is added tothe treating composition.

42. The process defined in claim 40 in which an anionic dye is added tothe treating composition.

43. The process as defined in claim 39 in which the mixture of filamentshas been dyed with a disperse dye prior to treatment with the treatingcomposition, said treating composition containing an anionic dye.

44. The process defined in claim 44 in which the mixture of filaments isdyed with a disperse dye after said treatment with the treatingcomposition defined therein.

45. The process defined in claim 39 in which the treating compositioncontains a viscosity increasing agent.

46. The process defined in claim 41 in which the treating compositioncontains a viscosity increasing agent.

47. The process as defined in claim 40 in which the mixture

2. The mixture of filaments defined in claim 1, in which the blendcontains between about 0.5 and 7 percent by weight of a hydrophiliccompound which is a homopolymer of ethylene oxide, an ether or esterderivative thereof, or copolymer of ethylene oxide, said hydrophiliccompound having a degree of polymerization not less than 4, and anethylene oxide content not less than 60 percent by weight, the totalamount of the thermoplastic nitrogen-containing polymer and saidhydrophilic compound in said blend being greater than 3 percent byweight of total blend.
 3. The mixture of filaments of claim 1 whereinthe poly(alpha-olefin) is selected from polyethylene, polypropylene,poly(3-methyl-1-butene) or poly(4-methyl-1-pentene) and the polyester isselected from the poly(ethyleneterephthalate),poly(1,4-cyclohexylene-dimethylene terephthalate).
 4. Themixture of filaments of claim 1 wherein the basic nitrogen-containingpolymer is selected from the group consisting of homopolymers ofvinylpyridines, alkylvinylpyridines, vinylquinolines,alkylvinylquinolines, or copolymers of vinylpyridine monomers with eachother or with alkylvinylpyridine monomers, or copolymers ofvinylpyridine monomers with a monoethylenically unsaturated monomer. 5.The mixture of filaments of claim 4 which is a yarn.
 6. The mixture offilaments of claim 4 which is a fabric.
 7. The mixture of filaments ofclaim 4 which is included in a carpet.
 8. The fabric of claim 6 whichcontains uncolored non-dye receptor-containing poly(alpha-olefin) orpolyester fibers which are not susceptible to dyeing by anionic anddisperse dyes under the conditions of dyeing.
 9. The carpet of claim 7which contains uncolored non-dye receptor-containing poly(alpha-olefin)or polyester fibers which are not susceptible to dyeing by anionic anddisperse dyes under the conditions of dyeing.
 10. The fabric of claim 6which contains pigmented poly(alpha-olefin) or polyester fibers whichare not susceptible to dyeing by anionic and disperse dyes under theconditions of dyeing.
 11. The carpet of claim 7 which contains pigmentedpoly(alpha-olefin) or polyester fibers which are not susceptible todyeing by anionic and disperse dyes under the cOnditions of dyeing. 12.The fabric of claim 8 which contains pigmented poly(alpha-olefin) orpolyester fibers which are not susceptible to dyeing by anionic anddisperse dyes under the conditions of dyeing.
 13. The carpet of claim 9which contains pigmented poly(alpha-olefin) or polyester fibers whichare not susceptible to dyeing by anionic and disperse dyes under theconditions of dyeing.
 14. The mixture of filaments defined in claim 4 inwhich the basic dye receptor polymers is selected from the groupconsisting of: a. poly(2-vinylpyridine) b.poly(2-methyl-5-vinylpyridine) c. poly(4-vinylpyridine) d.poly(2-vinylquinoline) e. the copolymer of 2-vinylpyridine and2-methyl-5-vinylpyridine f. the copolymer of 2-vinylpyridine and styrenee. the copolymer of 2-methyl-5vinylpyridine and styrene.
 15. The mixtureof filaments defined in claim 14 in which the poly(alpha-olefin) isselected from the group consisting of polyethylene, polypropylene,poly(3-methyl-1-butene) or poly(4-methyl-1-pentene) and the polyester isselected from the group consisting of poly(ethylene terephthalate),poly(ethylene terephthalate-isophthalate) orpoly(1,4-cyclohexylene-dimethylene terephthalate.)
 16. The mixture offilaments of claim 15 in which the Lewis acid or Lewis acid-generatingmaterial is selected from the group consisting of a. Concentratedinorganic acids, or their anhydrides b. Organo-carboxylic or sulfonicacids c. Hydrolyzable halides d. Borate esters e. Phenol
 17. The mixtureof filaments of claim 16 which has been treated under acid conditionswith an anionic surfactant either prior to or during said Lewis acid orLewis acid-generating material treatment, said anionic surfactant havingthe general formula R-A wherein: R represents a substituted orunsubstituted alkyl, aryl, or alkylaryl group having at least six carbonatoms and A represents an anionic group selected from (a) sulfate, (b)sulfonate, (c) phosphate, (d) polyphosphate or (e) carboxylate.
 18. Themixture of filaments of claim 17 which has been treated with a mixtureof 0.1 percent or greater of Lewis acid or Lewis acid-generatingmaterial based on the total treating composition weight, and greaterthan 0.5 percent of said anionic surfactant based on the total treatingcomposition weight and a viscosity increasing agent.
 19. The mixture offilaments of claim 18 in which said mixture contains an anionicdyestuff.
 20. The mixture of filaments of claim 19 which has been dyedwith an anionic or disperse dyestuff prior to treatment with saidmixture.
 21. The mixture of filaments of claim 2 wherein thepoly(alpha-olefin) selected from polyethylene, polypropylene,poly(3-methyl-1-butene) or poly(4-methyl-1-pentene) and the polyester isselected from poly(ethylene terephthalate), poly(ethyleneterephthalate-isophthalate) or poly(1,4-cyclohecylene-dimethyleneterephthalate).
 22. The mixture of filaments of claim 2 wherein thebasic nitrogen-containing polymer is selected from the group consistingof homopolymers of vinylpyridines, alkylvinylpyridines, vinylquinolines,alkylvinylquinolines, or copolymers of vinylpyridine monomers with eachother or with alkylvinylpyridine monomers, or copolymers ofvinylpyridine monomers with a monoethylenically unsaturated monomer. 23.The filamentary assembly of claim 22 which is a yarn.
 24. The mixture offilaments of claim 22 which is a fabric.
 25. The mixture of filaments ofclaim 22 which is included in a carpet.
 26. The fabric of claim 24 whichcontains uncolored non-dye receptor-containing poly(alpha-olefin) orpolyester fibers which are not susceptible to dyeing by anionic anddisperse dyes under the conditions of dyeing.
 27. The carpet of claim 25which contains uncolored non-dye receptor-containing poly(Alpha-olefin)or polyester fibers which are not susceptible to dyeing by anionic anddisperse dyes under the conditions of dyeing.
 28. The fabric of claim 24which contains pigmented poly(alpha-olefin) or polyester fibers whichare not susceptible to dyeing by anionic and disperse dyes under theconditions of dyeing.
 29. The carpet of claim 25 which containspigmented poly(alpha-olefin) or polyester fibers which are notsusceptible to dyeing by anionic and disperse dyes under the conditionsof dyeing.
 30. The fabric of claim 26 which contains pigmentedpoly(alpha-olefin) or polyester fibers which are not susceptible todyeing by anionic and disperse dyes under the conditions of dyeing. 31.The carpet of claim 27 which contains pigmented poly(alpha-olefin) orpolyester fibers which are not susceptible to dyeing by anionic anddisperse dyes under the conditions of dyeing.
 32. The mixture offilaments defined in claim 22 in which the basic dye receptor polymer isselected from the group consisting of: a. poly(2-vinylpyridine) b.poly(2-methyl-5-vinylpyridine) c. poly(4-vinylpyridine) d.poly(2-vinylquinoline) e. the copolymer of 2-vinylpyridine and2-methyl-5-vinylpyridine f. the copolymer of 2-vinylpyridine and styreneg. the copolymer of 2-methyl-5-vinylpyridine and styrene.
 33. The shapedarticle of claim 32 in which the poly(alpha-olefin) is selected from thegroup consisting of polyethylene, polypropylene, poly(3-methyl-1-butene)or poly(4-methyl-1-pentene) and the polyester is selected from the groupconsisting of poly(ethylene terephthalate), poly(ethyleneterephthalate-isophthalate) or poly(1,4-cyclohexylene-dimethyleneterephthalate).
 34. The mixture of filaments of claim 33 in which theLewis acid or Lewis acid-generating material is selected from the groupconsisting of a. Concentrated inorganic acids or their anhydrides. b.Organo-carboxylic or sulfonic acids. c. Hydrolyzable halides. d. Borateesters. e. Phenol.
 35. The mixture of filaments of claim 34 which hasbeen treated under acid conditions with an anionic surfactant eitherprior to or during said Lewis acid or Lewis acid generating materialtreatment, said anionic surfactant having the general formula R-Awherein: R represents a substituted or unsubstituted alkyl, aryl, oralkylaryl group having at least six carbon atoms and A represents ananionic group selected from (a) sulfate, (b) sulfonate, (c) phosphate,(d) polyphosphate or (e) carboxylate.
 36. The mixture of filaments ofclaim 35 which has been treated with a mixture of 0.1 percent or greaterof Lewis acid or Lewis acid-generating material based on the totaltreating composition weight, and greater than 0.5 percent of saidanionic surfactant based on the total treating composition weight and aviscosity increasing agent.
 37. The mixture of filaments of claim 36 inwhich said mixture contains an anionic dyestuff.
 38. The mixture offilaments of claim 37 which has been dyed with an anionic or dispersedyestuff prior to treating with said mixture.
 39. A process for makingthe mixture of filaments defined in claim 1 comprising the followingsteps in sequence: a. blending between about 0.5 and 5 percent of athermoplastic nitrogen-containing basic polymer capable of bindinganionic dyes with a fiber-forming poly(alpha-olefin) or polyester, b.forming the resulting blend into fiber, c. forming said fiber into amixture of filaments, d. discontinuously contacting the surface of saidfilaments with a treating composition which contains between about 4 and100 percent of a Lewis acid or Lewis acid generating material, e.heating said mixture of filaments containing the treating compositionfor such time to allow penetration of same, f. removing the excesstreatIng composition, g. dyeing the treated filaments with an anionicdyestuff alone or in combination with a disperse dyestuff.
 40. Theprocess defined in claim 39, in which between about 0.5 and 7 percent byweight of a hydrophilic compound has been added to the blend prior toforming said blend into fiber, said hydrophilic compound being ahomopolymer of ethylene oxide, an ether or ester derivative thereof, orcopolymer of ethylene oxide, said hydrophilic compound having a degreeof polymerization not less than 4, and an ethylene oxide content notless than 60 percent by weight, the total amount of the thermoplasticnitrogen containing polymer and hydrophilic compound in said blend beinggreater than 3 percent by weight of the total blend.
 41. The processdefined in claim 39 in which an anionic dye is added to the treatingcomposition.
 42. The process defined in claim 40 in which an anionic dyeis added to the treating composition.
 43. The process as defined inclaim 39 in which the mixture of filaments has been dyed with a dispersedye prior to treatment with the treating composition, said treatingcomposition containing an anionic dye.
 44. The process defined in claim41 in which the mixture of filaments is dyed with a disperse dye aftersaid treatment with the treating composition defined therein.
 45. Theprocess defined in claim 39 in which the treating composition contains aviscosity increasing agent.
 46. The process defined in claim 41 in whichthe treating composition contains a viscosity increasing agent.
 47. Theprocess as defined in claim 40 in which the mixture of filaments hasbeen dyed with a disperse dye prior to treatment with the treatingcomposition, said treating composition containing an anionic dye. 48.The process defined in claim 42 in which the mixture of filaments isdyed with a disperse dye after said treatment with the treatingcomposition defined therein.
 49. The process defined in claim 40 inwhich the treating composition contains a viscosity increasing agent.50. The process defined in claim 42 in which the treating compositioncontains a viscosity increasing agent.